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PRISHCHENKO et al.
The obtained compounds of chelate type I–VIII
(MeО). 31Р NMR spectrum, δ, ppm: 20.74. Found, %:
С 60.59; Н 5.73. С42Н48N4О10P2. Calculated, %: С
60.72; Н 5.82.
include carbonyl and phosphoryl groups along with the
fragments of pyridine and 2,6-di-tert-butylphenol.
They are of interest as effective polydentate ligands
and also as promising antioxidants.
1,3-Bis{N-phenyl-N-[3,5-di-tert-butyl-4-hydroxy-
phenyl(diethoxyphosphoryl)methyl]aminocarbonyl}-
benzene (III). Yield 86%, mp 65°С. First isomer,
content 95%. 1H NMR spectrum, δ, ppm: 4.88 d (С1H,
2JPH 20 Hz), 5.70 br.s (ОН), 1.42 s (t-Bu). 13С NMR
The NMR spectra of compounds I–VIII contain
characteristic signals of fragments РС1HN(C2)C3(O)
1
whose parameters are given below. In the H and 13C
NMR spectra signals of aromatic fragments of these
compounds are partially or fully overlapped. Com-
pounds I–VIII consist of two stereoisomers. The
1
spectrum, δ, ppm: 54.62 d (С1, JPС 151 Hz), 147.97 d
3
(С2, JPС 14 Hz), 165.53 (С3), 153.62 (САrОН), 30.33
and 34.87 (t-Bu). 31Р NMR spectrum, δ, ppm: 23.67.
Second isomer: 31Р NMR spectrum, δ, ppm: 20.86.
Found, %: С 67.81; Н 7.54. С58Н78N2О10P2. Cal-
culated, %: С 67.95; Н 7.67.
1
content of them was determined by the H and 31P
NMR spectroscopy. Only the 31Р NMR spectra param-
eters are given for the Second isomers of compounds
III, IV, VI, and VII due to the low content of these
isomers.
1,3-Bis{N-pyrid-2-yl-N-[3,5-di-tert-butyl-4-hyd-
roxyphenyl(diethoxyphosphoryl)methyl]aminocar-
bonyl}benzene (IV). Yield 89%, mp 94°С. First
isomer, content 95%. 1H NMR spectrum, δ, ppm: 6.39
1,3-Bis{N-methyl-N-[4-anisyl(diethoxyphosphoryl)-
methyl]aminocarbonyl}benzene (I). To a solution of
6 g of anisal(methyl)amine in 15 ml of methylene
chloride was dropwise added 4.06 g of isophthaloyl
chloride in 10 ml of methylene chloride at 0°С under
stirring. After 1 h to this mixture was added a solution
of 8.5 g of diethyl(trimethylsilyl)phosophite in 10 ml
of methylene chloride. The mixture was stirred for 2 h
at 20°С. The solvent was removed, and to the residue
was added 3 ml of hexane. This mixture was cooled to
–10°С. The solvent was decanted, and the precipitated
crystals were kept in a vacuum of 0.5 mm Hg for 1 h.
Yield 12.5 g, 89%, mp 59°С. First isomer, content
2
d (С1H, JPH 24 Hz), 5.72 br.s (ОН), 1.41 s (t-Bu). 13С
1
NMR spectrum, δ, ppm: 57.61 d (С1, JPС 159 Hz),
160.46 (С2), 165.76 (С3), 154.10 (САrОН), 30.33 and
34.87 (t-Bu). 31Р NMR spectrum, δ, ppm: 21.36.
Second isomer: 31Р NMR spectrum, δ, ppm: 21.80.
Found, %: С 65.43; Н 7.39. С56Н76N4О10P2. Cal-
culated, %: С 65.48; Н 7.46.
1,4-Bis{N-methyl-N-[4-anisyl(diethoxyphosphoryl)-
methyl]aminocarbonyl}benzene (V). Yield 92%, mp
83°С. First isomer, content 80%. 1H NMR spectrum, δ,
1
2
75%. H NMR spectrum, δ, ppm: 6.30 d (С1H, JPH
2
ppm: 6.47 d (С1H, JPH 20 Hz), 2.91 s (MeN), 3.81 s
24 Hz), 2.78 s (MeN), 3.59 s (MeО). 13С NMR
13
(MeО). С NMR spec-trum, δ, ppm: 52.52 d (С1, 1JPС
spectrum, δ, ppm: 52.42 d (С1, JPС 157 Hz), 34.29
1
157 Hz), 34.42 (С2), 171.19 (С3), 55.23 (MeО). 31Р
(С2), 170.21 (С3), 55.03 (MeО), 159.60 (СArО). 31Р
1
NMR spectrum, δ, ppm: 23.56. Second isomer: H
1
NMR spectrum, δ, ppm: 20.50. Second isomer: H
NMR spectrum, δ, ppm: 4.45 d (С1H, 2JPH 20 Hz), 2.86
(MeN), 3.78 (MeО). 13С NMR spectrum, δ, ppm:
NMR spectrum, δ, ppm: 4.92 d (С1H, 2JPH 24 Hz), 2.69 s
(MeN), 3.59 s (MeО). 13С NMR spectrum, δ, ppm:
1
59.33 d (С1, JPС 156 Hz), 34.78 (С2), 171.67 (С3),
59.25 d (С1, JPС 155 Hz), 30.81 (С2), 166.95 (С3),
1
55.23 (MeО). 31Р NMR spectrum, δ, ppm: 23.84.
Found, %: С 57.69; Н 6.52. С34Н46N2О10P2. Cal-
culated, %: С 57.95; Н 6.58.
55.03 (MeО), 159.60 (СArО). 31Р NMR spectrum, δ, ppm:
20.12. Found, %: С 57.78; Н 6.49. С34Н46N2О10P2.
Calculated, %: С 57.95; Н 6.58.
1,4-Bis{N-pyrid-2-yl-N-[4-anisyl(diethoxyphos-
phoryl)methyl]aminocarbonyl}benzene (VI). Yield
1,3-Bis{N-pyrid-2-yl-N-[4-anisyl(diethoxyphos-
phoryl)methyl]aminocarbonyl}benzene (II). Yield
1
1
90%, mp 91°С. First isomer, content 95%. H NMR
87%, mp 131°С. First isomer, content 60%. H NMR
2
spectrum, δ, ppm: 5.92 d (С1H, JPH 24 Hz), 3.83 s
spectrum, δ, ppm: 5.80 d and 5.82 d (С1H, 2JPH 20 and
24 Hz), 3.70 s (MeО). 13С NMR spectrum, δ, ppm:
1
(MeО). 13С NMR spectrum, δ, ppm: 50.66 d (С1, JPС
154 Hz), 157.54 d (С2, 3JPС 9 Hz), 168.5 s (С3), 55.13 s
(MeО), 159.31 s (САrО). 31Р NMR spectrum, δ, ppm:
23.47. Second isomer: 31Р NMR spectrum, δ, ppm:
20.98. Found, %: С 60.64; Н 5.74. С42Н48N4О10P2.
Calculated, %: С 60.72; Н 5.82.
1
50.61 d (С1, JPС 155 Hz), 172.10 (С3), 55.48 (MeО).
1
31Р NMR spectrum, δ, ppm: 23.27. Second isomer: H
2
NMR spectrum, δ, ppm: 5.26 d and 5.28 d (С1H, JPH
20 and 24 Hz), 3.70 s (MeО). 13С NMR spectrum, δ,
1
ppm: 58.63 d (С1, JPС 158 Hz), 172.70 (С3), 55.39
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 1 2010